EP1379616B1 - Fluide hydraulique de tracteur tous temps faisant appel a un melange de types de modificateur de viscosite satisfaisant aux exigences de viscosite multigrade antivaporisation - Google Patents

Fluide hydraulique de tracteur tous temps faisant appel a un melange de types de modificateur de viscosite satisfaisant aux exigences de viscosite multigrade antivaporisation Download PDF

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Publication number
EP1379616B1
EP1379616B1 EP02719458A EP02719458A EP1379616B1 EP 1379616 B1 EP1379616 B1 EP 1379616B1 EP 02719458 A EP02719458 A EP 02719458A EP 02719458 A EP02719458 A EP 02719458A EP 1379616 B1 EP1379616 B1 EP 1379616B1
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weight
carbon atoms
composition
viscosity
viscosity modifier
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EP1379616A1 (fr
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Richard E. Gapinski
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Lubrizol Corp
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Lubrizol Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/10—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aromatic monomer, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C10M157/04—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • C10M2217/023—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group the amino group containing an ester bond
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the present invention relates to a functional fluid, such as a tractor hydraulic fluid, which exhibits shear stable viscosity characteristics and has a wide temperature range of operation.
  • U.S. Patent 6,133,210, Tipton discloses concentrates for preparing lubricating oil compositions such as automatic transmission fluids.
  • the viscosity index improver can be at least one of a polyacrylate ester copolymer, optionally containing nitrogen-containing groups; and an esterified carboxy-containing interpolymer, where one of the monomers is a vinyl aromatic monomer and the other monomer is an alpha, beta-unsaturated acylating agent.
  • the polyacrylate ester can have a Mn of 20,000 to about 100,000.
  • the esterified carboxy-containing interpolymer can have an RSV of 0.05 to 0.35.
  • U.S. Patent 6,124,249 discloses viscosity improvers for lubricating oil compositions, being a copolymer with units of methacrylic acid esters containing 7-12 and 13-19 carbon atoms in the ester group; and a comonomer that can be dimethylaminopropylmethacrylamide.
  • Auxiliary viscosity improvers can also be included in the lubricating composition, including esterified styrene-maleic anhydride copolymers (col. 16).
  • the molecular weight (M ⁇ w ) of the acrylic copolymer is listed as 20,000 to 120,000
  • U.S. Patent 5,646,099, Watts et al. discloses an automatic transmission fluid of improved viscometric properties, containing (among other components) 0.05 to 2.0 weight percent of a flow improver selected from the group consisting of C 8 to C 18 dialkylfumarate vinyl acetate copolymers, styrene-maleic anhydride copolymers, polymethacrylates, polyacrylates, and their mixtures.
  • a flow improver selected from the group consisting of C 8 to C 18 dialkylfumarate vinyl acetate copolymers, styrene-maleic anhydride copolymers, polymethacrylates, polyacrylates, and their mixtures.
  • EP 0 204 587 A discloses a lubricating oil composition containing a dual additive combination for reducing the low temperature viscosity properties thereof.
  • the additive combination comprises a polymethacrylate or esterified styrene/maleic anhydride copolymer and a sorbitan tristearate.
  • the present invention therefore, solves the problem of providing low temperature fluidity, high temperature viscosity and shear stability in a fluid by using two types of viscosity modifiers: a polymethacrylate ester and an ester of a maleic anhydride/styrene copolymer.
  • a polymethacrylate ester and an ester of a maleic anhydride/styrene copolymer.
  • Such fluids are useful in a variety of climatic conditions.
  • the fluids of the present invention are advantageously used as tractor hydraulic fluids and can also be used as a variety of other functional fluids, including manual transmission fluids, automatic transmission fluids (including fluids for continuously variable transmissions and traction drives) and other hydraulic fluids. They can also be used in other lubricating applications such as gear oils and engine oils.
  • the present invention provides a composition suitable for use as a functional fluid in a variety of climatic conditions, comprising the following components:
  • the invention further comprises a concentrate comprising:
  • the invention further provides a method for lubricating a tractor or off-road vehicle, comprising supplying thereto the composition described above.
  • Component (a) is base oil of lubricating viscosity.
  • lubricating oils include natural oils and synthetic oils.
  • Natural oils include animal oils and vegetable oils (e.g., lard oil, castor oil) as well as mineral lubricating oils such as liquid petroleum oils and solvent treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic/naphthenic types that may be further refined by hydrocracking, hydrofinishing, or dewaxing processes. Oils of lubricating viscosity derived from coal or shale are also useful. Useful natural base oils may be those designated by the American Petroleum Institute (API) as Group I, II, or III oils. Upon occasion, highly refined or hydrocracked natural oils have been referred to as "synthetic" oils.
  • API American Petroleum Institute
  • synthetic lubricating oils are understood to include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, poly(1-decenes)), alkyl-benzenes (e.g., dodecylbenzenes); polyphenyls; alkylated diphenyl ethers, and alkylated diphenyl sulfides.
  • Polyalpha olefin oils are also referred to as API Group IV oils.
  • Other suitable oils include those prepared by Pischer-Tropsch syntheses.
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified such as by esterification or etherification constitute another class of known synthetic lubricating oils.
  • Other synthetic lubricating oils include esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, ethylene glycol). Silicon-based oils such as siloxane oils and silicate oils comprise another useful class of synthetic lubricants.
  • Other synthetic lubricating oils include liquid esters of phosphorus-containing acids.
  • traction oils are typically synthetic fluids containing a large fraction of highly branched or cycloaliphatic structures, i.e., cyclohexyl rings. Traction oils or traction fluids are described in detail, for example, in U.S. Patents 3,411,369 and 4,704,490.
  • Unrefined, refined, and re-refined oils can be used.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
  • Re-refined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service.
  • the amount of component (a) in the compositions of the present invention is generally 70 to 93% by weight. Preferably the amount of component (a) is 72-88%. More preferably the amount of component (a) is 75-87%.
  • Components (b) and (c) are two viscosity modifiers, each having defined compositions and molecular weights.
  • Component (b) is a polyacrylate or polymethacrylate and component (c) is a polymer comprising vinyl aromatic units and esterified carboxyl-containing units.
  • Component (b) is the lower molecular weight polymer, and component (c) is the higher molecular weight polymer.
  • Component (b) is preferably a polyacrylate, preferably polymethacrylate, dispersant viscosity modifier.
  • This is typically a copolymer that preferably comprises units derived from both (i) methacrylic acid esters containing 8 to 24 (preferably 10 to 18) carbon atoms in the alcohol moiety of the ester group and (ii) methacrylic acid esters containing 1 to 12 or 6 to 12 (preferably 8 to 10) carbon atoms in the alcohol moiety of the ester group, where the number of carbon atoms in (i) is greater than the number of carbon atoms in (ii).
  • the ester groups in (ii) typically have 2-(C 1-4 alkyl)-substituents, that is, branching, on the alcohol moiety.
  • polymers having only a single type of ester group may also be suitable.
  • the polymer also comprises (iii) at least one monomer selected from the group consisting of: methacrylic acid esters containing 1 to 10 (preferably 2 to 8) carbon atoms in the alcohol moiety of the ester group and which are different from methacrylic acid esters (i) and (ii); vinyl aromatic compounds; and nitrogen-containing vinyl monomers. Examples of the latter are methacrylamide and N-alkyl-substituted methacrylamides, as well as others described below.
  • esters in group (i) can contain 12 or 13 to 16 carbon atoms in the alcohol portion of the ester group, and those in group (ii) can contain 8 or 9 to 12 carbon atoms in the alcohol portion of the ester group.
  • a preferred example of ester (ii) is 2-ethylhexyl methacrylate.
  • Alcohols that are useful for preparing ester (i) typically contain 8 to 24 carbon atoms, preferably 12 to 15 carbon atoms. Mixtures of alcohols are commercially available and are frequently preferred.
  • the alcohols used to prepare ester (i) can be linear or branched. In one embodiment, 2 to 65% of the alcohols are branched, and frequently 5 to 60% are branched.
  • alcohols useful to prepare ester (i) include n-octanol, n-decanol, n- and branched- C 12 , C 15 , C 16 , and C 22 alcohols, mixtures of alcohols, e.g., C 12-15 alcohols available under the tradenames Dobanol TM 25, Neodol TM 25, Lial TM 125, and Alchem TM 125, that have varying degrees of branching, for example, 5% to 50% branching, or even more, and Alfol TM 1214, which is substantially linear.
  • Alcohols that are useful for preparing ester (ii) typically contain 6 to 11 carbon atoms, preferably 8 to 11, and most preferably 8 carbon atoms. These alcohols normally have a 2-(C 1-4 alkyl) substituent, namely, methyl, ethyl, or any isomer of propyl or butyl.
  • Examples of alcohols useful for preparing ester (ii) include 2-methylheptanol, 2-methyldecanol, 2-ethylpentanol, 2-ethylhexanol, 2-ethyl nonanol, 2-propyl heptanol, and 2-butyl heptanol.
  • the mole ratio of esters (i) to esters (ii) within the polymer is typically within the range of 95:5 to 35:65.
  • Useful nitrogen containing monomers include those selected from the group consisting of vinyl-substituted nitrogen heterocyclic monomers, for example vinyl pyridine and N-vinyl-substituted nitrogen heterocyclic monomers such as N-vinyl imidazole, N-vinyl pyrrolidinone, and N-vinyl caprolactam; dialkylaminoalkyl acrylate and methacrylate monomers, for example N,N-dialkylaminoalkyl acrylates such as dimethylaminoethyl methacrylate; dialkylaminoalkyl acrylamide and methacrylamide monomers, for example di-lower alkylaminoalkylacrylamide, especially where each alkyl or aminoalkyl group contains 1 to 8 carbon atoms, especially 1 to 3 carbon atoms, such as N,N-di lower alkyl, especially, dimethylaminopropylacrylamide, N-tertiary alkyl acrylamides and corresponding methacrylamides
  • this type of component include those prepared from mixtures of methacrylate monomers having different alkyl groups that are either straight chain or branched chain groups containing from 1 to 18 carbon atoms, and preferably copolymerized with a small amount of nitrogen-containing monomer such as vinyl pyridine, N-vinyl pyrrolidone, N,N'-dimethylaminoethyl methacrylate, or N,N'-dimethylaminopropyl methacrylamide.
  • nitrogen-containing monomer such as vinyl pyridine, N-vinyl pyrrolidone, N,N'-dimethylaminoethyl methacrylate, or N,N'-dimethylaminopropyl methacrylamide.
  • component (b) can be a copolymer comprising units derived from (i) 5% to 75% by weight of alkyl acrylate ester monomers containing 1 to 11 carbon atoms in the alkyl group; (ii) 25% to 95% by weight of alkyl acrylate ester monomers containing 12 to 24 carbon atoms in the alkyl group; and (iii) 0.1% to 20% by weight of at least one nitrogen-containing monomer selected from the group consisting of vinyl-substituted nitrogen heterocyclic monomers, N,N-dialkylaminoalkyl acrylate monomers, N,N-dialkylaminoalkyl acrylamide monomers and tertiary-alkyl acrylamides, provided that the total equals 100%.
  • a representative polymer 60 to 80% by weight (typically about 68%) of the monomers are C 12 to C 15 alkyl methacrylate, 20 to 40% (typically about 30%) 2-ethylhexylmethacrylate, and 1-5% (typically about 2%) of the monomers are dimethylaminopropylmethacrylamide.
  • the weight average molecular weight of the polymer of (b) (of whichever species) as determined by gel permeation chromatography is typically 10,000 to 60,000, preferably 25,000 to 50,000, or 30,000 to 40,000, or 32,000 to 36,000 or 33,000 to 34,000. Approximately corresponding number average molecular weights are, broadly, 10,000 to 300,000, more often 15,000 to 30,000, typically 17,000 to 19,000.
  • the amount of component (b) in the compositions of the present invention is 4-12% or preferably 5-10%.
  • Component (c) is a copolymer of a vinyl aromatic monomer and an esterified carboxy-containing monomer.
  • Suitable vinyl aromatic monomers include styrene and the substituted styrenes, although other vinyl aromatic monomers can also be used.
  • the substituted styrenes include styrenes that have halo-, amino-, alkoxy-, carboxy-, hydroxy-, sulfonyl-, hydrocarbyl- wherein the hydrocarbyl group has from 1 to about 12 carbon atoms and other substituents.
  • hydrocarbyl-substituted styrenes are alpha-methylstyrene, para-tert-butylstyrene, alpha-ethylstyrene, and para-lower alkoxy styrene. Mixtures of two or more vinyl aromatic monomers can be used. Styrene is preferred.
  • the carboxy-containing monomer is polymerized with vinyl aromatic monomer to form a carboxy-containing interpolymer. Since the carboxy-containing monomer is incorporated into the polymer backbone, the carboxy groups extend from the polymer backbone, e.g., the carboxy groups are directly attached to the polymer backbone.
  • the copolymer may comprise ester monomers with a mixture of relatively longer chain alcohol derived moieties (8 or more carbon atoms, for example, mixed alcohols of 8 to 18 carbon atoms) and relatively shorter chain alcohol derived moieties (1 to 7 carbon atoms, for example, n-butanol).
  • relatively longer chain alcohol derived moieties 8 or more carbon atoms, for example, mixed alcohols of 8 to 18 carbon atoms
  • relatively shorter chain alcohol derived moieties (1 to 7 carbon atoms, for example, n-butanol.
  • a typical molar ratio of longer chain to shorter chain units is (70-95):(5-30).
  • an optional element in the esterified copolymer is an amino group derived from amino compounds, and particularly those having an average of from 1 to about 1.1 primary or secondary amino groups.
  • the amino compound is a polyamino compound having at least one mono-functional amino group.
  • An example of such amino compounds is aminopropylmorpholine.
  • Such amino groups can be present to neutralize residual acid functionality in the polymer and can serve to enhance the dispersability of such esters in lubricant compositions and additives for lubricant compositions.
  • the molar ratio of the carboxy groups of said interpolymer that are esterified to the carboxy groups neutralized through the conversion thereof to amino-containing groups is generally 85:15 to 99:1. A preferred ratio is about 95:5.
  • the linkage containing the carbonyl-amino group may be salt, imide, amide, or amidine functionality.
  • Typical polymers of the type of component (c) are esterified maleic anhydride/styrene copolymers.
  • the monomers are present in approximately a one-to-one ratio in the copolymer.
  • Specific examples of this type of component include those in which the alcohol reactants are chosen from those having from 4 to 18 carbon atoms, and the residual acidity after esterification is neutralized with an amine.
  • the foregoing polymers, mixtures thereof, and details of their preparation are described in greater detail in U.S. Patent 5,707,943 and in references cited therein.
  • the weight average molecular weight of the viscosity modifier of (c) is typically 50,000 to 200,000, preferably 100,000 to 130,000 (polystyrene standard). Approximately corresponding number average molecular weights can be 10,000 to 50,000, preferably 20,000 to 25,000.
  • the amount of component (c) in the compositions of the present invention is 1-5%. More preferably the amount of component (c) is 1.5-4%. Alternative embodiments include those with an upper limit of component (c) of 3 or 2.5 or 2.4 percent by weight. Certain commercially available forms of the polymer of (c) are provided with approximately 50% polymer and 50% diluent oil, if such materials are used, the amounts would be adjusted accordingly (e.g., to a broad range of 2-12%, and so on).
  • the total amount of components (b) and (c) in the composition will broadly be determined by the amounts set forth above individually for (b) and (c). The total of these components is 5-15%, or 8-12%, or 9-11% by weight.
  • Component (d) is a mixture of components, some or all of which are typically present in a fully formulated lubricant of the present type. However, such a mixture is not considered to be required in any particular detail in order for the formulation to exhibit the improved viscosity properties of the present invention.
  • Component (d) is a fully formulated additive package suitable to meet an original equipment manufacturer's requirements for a functional fluid of the type under consideration, such as a tractor hydraulic fluid. The details of such a package can be varied considerably in a manner well known to those skilled in the art of formulation of lubricating fluids. Such variations will be determined, in part, by the requirements of the specific equipment to receive the lubricant composition. Examples of additives and additive packages that have been used in tractor hydraulic fluids are disclosed in U.S. Patents 5,635,459 and 5,843,873.
  • this type of component typically include among other materials, metal-containing detergents, such as 1 - 2% (e.g. 1.41%) of a calcium-overbased sulfonate detergent; antioxidants or anti-wear agents, such as 1-2% (e.g., 1.69%) of a zinc dialkyldithiophosphate; 0.5 to 2% (e.g. 1.03%) of friction modifiers;, and 0.1 to 2 % (e.g., 0.25%) of a nitrogen-containing dispersant such as succinimide dispersants.
  • metal-containing detergents such as 1 - 2% (e.g. 1.41%) of a calcium-overbased sulfonate detergent
  • antioxidants or anti-wear agents such as 1-2% (e.g., 1.69%) of a zinc dialkyldithiophosphate
  • friction modifiers 0.5 to 2% (e.g. 1.03%)
  • friction modifiers e.g. 1.03%
  • nitrogen-containing dispersant such as succin
  • composition described above is typically prepared by adding components b, c and d to component a, the oil, and mixing at an appropriate temperature, such as approximately 60°C, until homogeneous.
  • the above components can be in the form of a fully formulated lubricant or in the form of a concentrate (that is, an additive package) within a smaller amount of lubricating oil. If they are present in a concentrate, their concentrations will generally be approximately an order of magnitude or more greater than in a final lubricant composition.
  • the amount of the oil of lubricating viscosity (a) can be 10-70 percent by weight, or 20-60 percent, or 30-50 percent; the amount of the first viscosity modifier (b) can be 20 to 80 percent by weight or 30-70 percent; and the amount of the second viscosity modifier (c) can be 10 to 60 percent by weight, or 20-50 percent.
  • the first step in carrying out the method of the present invention is to blend components a-c or a-d as described above. Thereafter the mixture typically is supplied to the fluid reservoir of the equipment to be lubricated, and thence to the moving parts of the equipment itself.
  • the polymethacrylate viscosity modifier is a mixed alkyl methacrylate copolymer containing a small amount of dimethylaminoproylmethacrylamide, as described above, except as indicated.
  • the esterified maleic anhydride/styrene copolymer is a material, as described above, which is esterified with a mixture of alcohols and further reacted with amine.
  • shear loss is somewhat higher than in other examples. It is believed that these values could be reduced to within the preferred range of less than 20 by reducing the total amount of viscosity modifier or the amount of the esterified styrene/maleic anhydride copolymer somewhat.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include:
  • hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
  • aliphatic e.g., alkyl or alkenyl
  • alicyclic e.g., cycloalkyl, cycloalkenyl
  • aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
  • substituted hydrocarbon substituents that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
  • hetero substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms.
  • Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
  • no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (9)

  1. Composition apte à l'utilisation comme fluide fonctionnel dans diverses conditions climatiques, comprenant les constituants suivants :
    (a) une huile de viscosité propre à la lubrification ;
    (b) 4 à 12 % en poids d'un modificateur de viscosité ayant une moyenne en poids du poids moléculaire de 10 000 à 60 000 ; et
    (c) 1 à 5 % en poids d'un second modificateur de viscosité, ayant une moyenne en poids du poids moléculaire supérieure à celle du constituant (b) et étant comprise dans l'intervalle de 50 000 à 200 000 ;
    dans laquelle le constituant (b) est un polyacrylate ou polyméthacrylate et le constituant (c) est un polymère comprenant des motifs aromatiques vinyliques et des motifs contenant des groupes carboxyle estérifiés et dans laquelle la quantité totale du constituant (b) et du constituant (c) est de 5 à 15 % en poids.
  2. Composition suivant la revendication 1, dans laquelle le constituant (b) est un polyméthacrylate et le constituant (c) est un polymère comprenant des motifs aromatiques vinyliques et des motifs contenant des groupes carboxyle estérifiés.
  3. Composition suivant la revendication 1 ou la revendication 2, dans laquelle le modificateur de viscosité consistant en polyacrylate ou polyméthacrylate est un polyméthacrylate qui comprend des motifs dérivés à la fois (i) d'esters d'acide méthacrylique contenant 8 à 24 atomes de carbone dans le groupement alcool du groupe ester et (ii) d'esters d'acide méthacrylique contenant 6 à 12 atomes de carbone dans le groupement alcool du groupe ester, le nombre d'atomes de carbone dans (i) étant supérieur au nombre d'atomes de carbone dans (ii).
  4. Composition suivant la revendication 3, dans laquelle le modificateur de viscosité consistant en polyacrylate ou polyméthacrylate comprend également (iii) au moins un monomère choisi dans le groupe consistant en : des esters d'acide méthacrylique contenant 1 à 10 atomes de carbone dans le groupement alcool du groupe ester et qui sont différents des esters d'acide méthacrylique (i) et (ii) ; des composés aromatiques vinyliques et des monomères vinyliques azotés.
  5. Composition suivant l'une quelconque des revendications précédentes, dans laquelle le copolymère comprenant des motifs aromatiques vinyliques et des motifs contenant des groupes carboxy estérifiés est un copolymère styrène/acide maléique estérifié dans lequel les groupements esters comprennent un mélange de groupements dérivés d'un alcool ayant 8 ou plus de 8 atomes de carbone et de groupements dérivés d'un alcool ayant 1 à 7 atomes de carbone.
  6. Composition suivant la revendication 5, dans laquelle le copolymère styrène/acide maléique estérifié comprend en outre un groupe amino dérivé d'un composé à fonction amino.
  7. Composition suivant l'une quelconque des revendications précédentes, comprenant en outre :
    (d) une formulation d'additifs qui confère au fluide la capacité à satisfaire les essais sur banc et essais dynamométriques et qui comprend au moins un constituant choisi dans le groupe consistant en des détergents contenant des métaux, des antioxydants, des agents anti-usure, des modificateurs de frottement et des dispersants azotés.
  8. Concentré comprenant :
    (a) 10 à 70 % en poids d'une huile de viscosité propre à la lubrification ;
    (b) 20 à 80 % en poids d'un modificateur de viscosité ayant une moyenne en poids du poids moléculaire de 10 000 à 60 000 ; et
    (c) 10 à 60 % en poids d'un second modificateur de viscosité ayant une moyenne en poids du poids moléculaire supérieure à celle du constituant (b) et étant de 50 000 à 200 000 ;
    dans lequel le constituant (b) est un polyacrylate ou polyméthacrylate et le constituant (c) est un polymère comprenant des motifs aromatiques vinyliques et des motifs contenant des groupes carboxyle estérifiés.
  9. Procédé pour lubrifier un tracteur ou véhicule tout terrain, comprenant l'alimentation de celui-ci avec la composition de l'une quelconque des revendications 1 à 7.
EP02719458A 2001-04-20 2002-04-04 Fluide hydraulique de tracteur tous temps faisant appel a un melange de types de modificateur de viscosite satisfaisant aux exigences de viscosite multigrade antivaporisation Expired - Lifetime EP1379616B1 (fr)

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US28537701P 2001-04-20 2001-04-20
US285377P 2001-04-20
PCT/US2002/010906 WO2002086036A1 (fr) 2001-04-20 2002-04-04 Fluide hydraulique de tracteur tous temps faisant appel a un melange de types de modificateur de viscosite satisfaisant aux exigences de viscosite multigrade antivaporisation

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EP (1) EP1379616B1 (fr)
JP (1) JP2004524432A (fr)
KR (1) KR20030087082A (fr)
AT (1) ATE332352T1 (fr)
AU (1) AU2002250537B2 (fr)
CA (1) CA2442590A1 (fr)
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WO (1) WO2002086036A1 (fr)

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JP5207599B2 (ja) * 2006-06-08 2013-06-12 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物
WO2008013844A2 (fr) * 2006-07-25 2008-01-31 General Vortex Energy, Inc. Système, appareil et procédé de combustion d'un métal et autres combustibles
US8026199B2 (en) * 2006-11-10 2011-09-27 Nippon Oil Corporation Lubricating oil composition
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AU2002250537B2 (en) 2007-07-12
EP1379616A1 (fr) 2004-01-14
US20040110647A1 (en) 2004-06-10
KR20030087082A (ko) 2003-11-12
DE60212951T2 (de) 2007-02-22
WO2002086036A1 (fr) 2002-10-31
DE60212951D1 (de) 2006-08-17
ATE332352T1 (de) 2006-07-15
JP2004524432A (ja) 2004-08-12
CA2442590A1 (fr) 2002-10-31
US7189682B2 (en) 2007-03-13

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